摘要：

Motivated by recent spectroscopic evidence for carbon-rich atmospheres on some transiting exoplanets, we investigate the influence of the C/O ratio on the chemistry, composition, and spectra of extrasolar giant planets both from a thermochemical equilibrium perspective and from consideration of disequilibrium processes like photochemistry and transport-induced quenching. We find that although CO is predicted to be a major atmospheric constituent on hot Jupiters for all C/O ratios, other oxygen-bearing molecules like H2O and CO2 are much more abundant when C/O 4, HCN, and C2H2 gain significantly in abundance when C/O > 1. Other notable species like N2 and NH3 that do not contain carbon or oxygen are relatively unaffected by the C/O ratio. Disequilibrium processes tend to enhance the abundance of CH4, NH3, HCN, and C2H2 over a wide range of C/O ratios. We compare the results of our models with secondary-eclipse photometric data from the Spitzer Space Telescope and conclude that (1) disequilibrium models with C/O ~ 1 are consistent with spectra of WASP-12b, XO-1b, and CoRoT-2b, confirming the possible carbon-rich nature of these planets; (2) spectra from HD 189733b are consistent with C/O  1, but as the assumed metallicity is increased above solar, the required C/O ratio must increase toward 1 to prevent too much H2O absorption; (3) species like HCN can have a significant influence on spectral behavior in the 3.6 and 8.0 μm Spitzer channels, potentially providing even more opacity than CH4 when C/O > 1; and (4) the very high CO2 abundance inferred for HD 189733b from near-infrared observations cannot be explained through equilibrium or disequilibrium chemistry in a hydrogen-dominated atmosphere. We discuss possible formation mechanisms for carbon-rich hot Jupiters, including scenarios in which the accretion of CO-rich, H2O-poor gas dominates the atmospheric envelope, and scenarios in which the planets accrete carbon-rich solids while migrating through disk regions inward of the snow line. The C/O ratio and bulk atmospheric metallicity provide important clues regarding the formation and evolution of the giant planets.

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